US7488855B2 - Method of isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose - Google Patents
Method of isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose Download PDFInfo
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- US7488855B2 US7488855B2 US11/574,515 US57451505A US7488855B2 US 7488855 B2 US7488855 B2 US 7488855B2 US 57451505 A US57451505 A US 57451505A US 7488855 B2 US7488855 B2 US 7488855B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
Definitions
- the present invention relates to a method of isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- 1,3-propanediol is also called trimethylene glycol, 1,3-dihydroxypropane or 1,3-propylene glycol and has a molecular weight of 76, a freezing point of ⁇ 27° C., a boiling point of 210° C. and a viscosity of 1.053 cP.
- 1,3-propanediol is a light yellow, very sticky, weak acidic, water-miscible liquid.
- 1,3-propanediol is a primary monomer of polytrimethylene terephthalate (3GT) that is high performance polyester having various applications in clothes, carpet, etc.
- 1,3-propanediol is a very important intermediate in the production of polyester, polyether and polyurethane.
- U.S. Pat. No. 5,008,473 discloses a method of purifying 1,3-propanediol produced by hydrolysis of acrolein by extracting the diol with cyclohexane.
- U.S. Patent Application Publication No. 2002/0133049 discloses a method of recovering 1,3-propanediol from a liquid composition using a cation exchange resin.
- 1,3-propanediol, 1,2-propanediol, glucose and glycerol do not have an ion exchange property, these cannot be isolated from one another. Thus, said method does not provide sufficiently high purity and yield of 1,3-propanediol.
- U.S. Pat. No. 6,428,992 discloses a method of isolating 1,3-propanediol using a cation exchange resin whose cation is selected from the group consisting of lanthanum, lead, iron, zinc and aluminum.
- cations are materials harmful or dangerous to the human body.
- Korean Patent Publication No. 2002-0037064 discloses a method of isolating 1,3-propanediol from a biological mixture using zeolite. However, there is no description regarding a specific purity of 1,3-propanediol.
- U.S. Pat. Nos. 5,527,973 and 6,361,983 disclose a method of isolating 1,3-propanediol using distillation. However, distillation requires high energy and is inefficient in the removal of 1,2-propandiol having a boiling point of 187.6° C.
- the present invention provides a method of efficiently isolating 1,3-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- the present invention also provides a method of efficiently isolating 1,3-propanediol and 1,2-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- a method of isolating 1,3-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose comprising:
- a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and leaving the solution alone to fractionate the compounds in a solvent layer and a water layer;
- a method of isolating 1,3-propanediol and 1,2-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose comprising:
- a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and leaving the solution alone to fractionate the compounds in a solvent layer and a water layer.
- FIG. 1 is a HPLC analysis result of a solution containing 1,3-propanediol, 1,2-propanediol, glucose and glycerol;
- FIGS. 2A through 2D are graphs illustrating the solubility of each of 1,3-propanediol, 1,2-propanediol, glycerol, and glucose in ethyl acetate (EA);
- FIGS. 3 through 5 are chromatograms of 40 mL, 60 mL and 20 mL of a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2) in EA (the concentration of 1,3-propanediol in EA: 40 g/L); and
- FIGS. 6 through 8 are chromatograms of 40 mL, 60 mL and 80 mL of a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2) in methyl ethyl ketone (MEK) (the concentration of 1,3-propanediol in MEK: 40 g/L).
- MEK methyl ethyl ketone
- a method of isolating 1,3-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose includes: obtaining a concentrate by concentrating the solution via reduced pressure evaporation; dissolving the concentrate in a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and leaving the solution alone to fractionate the compounds in a solvent layer and a water layer; and loading the solvent layer in a silica-filled column under a low pressure liquid chromatography condition and eluting the solvent layer with a mixed solvent of methanol and at least one solvent which is miscible with methanol and has a polarity lower than methanol.
- a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose is concentrated by reduced pressure evaporation to remove water.
- the obtained concentrate is dissolved in a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and left alone to fractionate the compounds in a solvent layer and a water layer.
- the amount of the concentrate dissolved in the solvent is such that the concentration of 1,3-propanediol in the solvent is 5-100 g/L, preferably 35-45 g/L.
- 1,3-propanediol, 1,2-propanediol, glycerol, and glucose in the solution are distributed in the solvent layer and the water layer according to their solubility in the solvent and water. Most of 1,3-propanediol and 1,2-propanediol is distributed in the solvent layer and glucose and a part of glycerol are distributed in the water layer. Thus, by taking the solvent layer, 1,3-propanediol and 1,2-propanediol containing no glucose and a part of glycerol can be first isolated from the solution.
- the obtained solvent layer is loaded in a silica-filled column under a low pressure liquid chromatography condition and is eluted with a mixed solvent of methanol and at least one solvent which is miscible with methanol and has a polarity lower than methanol to finally isolate 1,3-propanediol from the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- the low pressure liquid chromatography takes place at a relatively low pressure, for example, at about 120 psi or less, in contrast to a high pressure liquid chromatography (HPLC).
- the solvent miscible with methanol and having a polarity lower than methanol may be selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof.
- Methanol and at least one solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof may be mixed in a ratio of 90:10 to 99.9:0.9, preferably 97:3 to 99:1.
- a method of isolating 1,3-propanediol and 1,2-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose includes: obtaining a concentrate by concentrating the solution via reduced pressure evaporation; and dissolving the concentrate in a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and leaving the solution alone to fractionate the compounds in a solvent layer and a water layer.
- a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose is concentrated by reduced pressure evaporation to remove water.
- the obtained concentrate is dissolved in a solvent selected from the group consisting of ethyl acetate, methyl ethyl ketone, and a mixture thereof and left alone to fractionate the compounds in a solvent layer and a water layer.
- the amount of the concentrate dissolved in the solvent is such that the concentration of 1,3-propanediol in the solvent is 5-100 g/L, preferably 35-45 g/L.
- 1,3-propanediol, 1,2-propanediol, glycerol, and glucose in the solution are distributed in the solvent layer and the water layer according to their solubility in the solvent and water. Most of 1,3-propanediol and 1,2-propanediol is distributed in the solvent layer and glucose and a part of glycerol are distributed in the water layer. Thus, by taking the solvent layer, 1,3-propanediol and 1,2-propanediol containing no glucose and a part of glycerol can be isolated from the solution.
- a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2) was evaporated under reduced pressure at a temperature of 80° C. or higher to remove water, thereby obtaining a concentrate.
- the obtained concentrate was completely dried and dissolved in water. Then, the solution was analysed through HPLC under the conditions given in Table 1. The HPLC results were given in Table 1.
- FIGS. 2A through 2D are graphs illustrating the solubility of each of 1,3-propanediol, 1,2-propanediol, glycerol, and glucose in EA.
- the solubility of 1,3-propanediol was about 40 g/L and solubilities of 1,2-propanediol and glycerol were 5-7 g/L and 3-6 g/L, respectively.
- glucose can be removed from the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- glucose can be removed from the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- a silica resin (size 0.040-0.063 mm, MERCK) was filled in a column with a diameter of 2 cm and a length of 180 cm and was stabilized using a 98:2 mixture of EA and methanol (MeOH) as a mobile phase.
- a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2) in EA was prepared such that the concentration of 1,3-propanediol in EA was 40 g/L.
- the solution was loaded in the column in sample volumes of 40 mL, 60 mL and 20 mL.
- FIGS. 3 through 5 are chromatograms of 40 mL, 60 mL and 20 mL of the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2).
- FIG. 3 through 5 are chromatograms of 40 mL, 60 mL and 20 mL of the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2).
- a, b, c , and d respectively designate points at 70, 75, 80 and 85 minutes after starting elution. When fractions were recovered after these points, the yield and purity of 1,3-propanediol were 96% and 94%, 92% and 95%, 82% and 98%, and 64% and 100%, respectively.
- a, b, c , and d respectively designate points at 65, 70, 75 and 80 minutes after starting elution. When fractions were recovered after these points, the yield and purity of 1,3-propanediol were 81% and 91%, 78% and 94%, 66% and 98%, and 42% and 100%, respectively.
- FIG. 1 In FIG.
- a silica resin (size 0.040-0.063 mm, MERCK) was filled in a column with a diameter of 2 cm and a length of 180 cm and was stabilized using a 98:2 mixture of methyl ethyl ketone (MEK) and methanol (MeOH) as a mobile phase.
- MEK methyl ethyl ketone
- MeOH methanol
- MEK methyl ethyl ketone
- MeOH methanol
- FIGS. 6 through 8 are chromatograms of 40 mL, 60 mL and 80 mL of the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2).
- FIG. 6 through 8 are chromatograms of 40 mL, 60 mL and 80 mL of the solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose (10:1:2:2).
- a, b, c, D , and e respectively designate points at 45, 50, 55, 60 and 65 minutes after starting elution.
- the yield and purity of 1,3-propanediol were 79% and 94%, 76% and 95%, 48% and 96%, 26% and 98%, and 13% and 100%, respectively.
- a, b, c , and d respectively designate points at 45, 50, 55 and 60 minutes after starting elution.
- the yield and purity of 1,3-propanediol were 91% and 91%, 81% and 92%, 51% and 98%, and 26% and 100%, respectively.
- 1,3-propanediol can be efficiently isolated from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
- 1,3-propanediol and 1,2-propanediol containing no glucose and a part of glycerol can be efficiently isolated from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Saccharide Compounds (AREA)
Abstract
Description
TABLE 1 | |||
Apparatus | HPLC (Waters) | ||
Column | ID 6.5 mm × L 300 mm | ||
Filler | Sugar-Pak (Waters) | ||
|
90° C. | ||
Mobile phase | Distilled water | ||
Flow rate | 0.5 mL/ | ||
Injection volume | |||
20 μl | |||
Solvent | Distilled water | ||
Claims (5)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020040069565A KR100629772B1 (en) | 2004-09-01 | 2004-09-01 | A method for isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from a solution containing 1,3-propanediol, 1,2-propanediol, glycerol and glcuose |
KR10-2004-0069565 | 2004-09-01 | ||
PCT/KR2005/002890 WO2006025697A1 (en) | 2004-09-01 | 2005-09-01 | Method of isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose |
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US20080097130A1 US20080097130A1 (en) | 2008-04-24 |
US7488855B2 true US7488855B2 (en) | 2009-02-10 |
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US11/574,515 Active 2026-02-02 US7488855B2 (en) | 2004-09-01 | 2005-09-01 | Method of isolating 1,3-propanediol or 1,3-propanediol and 1,2-propanediol from solution containing 1,3-propanediol, 1,2-propanediol, glycerol, and glucose |
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US (1) | US7488855B2 (en) |
KR (1) | KR100629772B1 (en) |
CN (1) | CN101010272B (en) |
BR (1) | BRPI0514743B1 (en) |
WO (1) | WO2006025697A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110060168A1 (en) * | 2008-03-02 | 2011-03-10 | Molzahn David C | Improved hydrogenation process |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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ES2388754T3 (en) * | 2007-11-30 | 2012-10-18 | Metabolic Explorer | Procedure for the purification of an alcohol from a fermentation broth |
KR101134619B1 (en) * | 2009-12-10 | 2012-04-09 | 한국과학기술연구원 | Method for purifying 1,3-propanediol |
WO2012130316A1 (en) | 2011-03-31 | 2012-10-04 | Metabolic Explorer | Method for purifying mpg (monopropylene glycol) from a fermentation broth |
KR102391893B1 (en) * | 2017-03-10 | 2022-04-28 | 엘지이노텍 주식회사 | Liquid lens, camera module and optical device/instrument including the same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5008473A (en) | 1986-09-24 | 1991-04-16 | Ruhrchemie Aktiengesellschaft | Process for purifying propanediol-1,3 |
US5527973A (en) | 1994-12-16 | 1996-06-18 | Kelsey; Donald R. | Purification of 1,3-propanediol |
WO1996035795A1 (en) | 1995-05-12 | 1996-11-14 | E.I. Du Pont De Nemours And Company | Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase |
WO2001025178A1 (en) | 1999-10-05 | 2001-04-12 | E.I. Du Pont De Nemours And Company | Process to separate 1,3-propanediol or glycerol, or a mixture thereof from a biological mixture |
US6361983B1 (en) | 1999-09-30 | 2002-03-26 | E. I. Du Pont De Nemours And Company | Process for the isolation of 1,3-propanediol from fermentation broth |
US6428992B1 (en) | 1999-11-16 | 2002-08-06 | Roquette Freres | Process for the purification of 1,3-propanediol from a fermentation medium |
US20020133049A1 (en) | 2000-03-29 | 2002-09-19 | Archer-Daniels-Midland Company | Method of recovering 1,3-propanediol from fermentation broth |
JP2004229660A (en) | 2003-01-07 | 2004-08-19 | Osaka Industrial Promotion Organization | New protein and method for preparation of arabinobiose using the same |
-
2004
- 2004-09-01 KR KR1020040069565A patent/KR100629772B1/en active IP Right Grant
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2005
- 2005-09-01 BR BRPI0514743-3A patent/BRPI0514743B1/en active IP Right Grant
- 2005-09-01 US US11/574,515 patent/US7488855B2/en active Active
- 2005-09-01 CN CN2005800294339A patent/CN101010272B/en active Active
- 2005-09-01 WO PCT/KR2005/002890 patent/WO2006025697A1/en active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5008473A (en) | 1986-09-24 | 1991-04-16 | Ruhrchemie Aktiengesellschaft | Process for purifying propanediol-1,3 |
US5527973A (en) | 1994-12-16 | 1996-06-18 | Kelsey; Donald R. | Purification of 1,3-propanediol |
WO1996035795A1 (en) | 1995-05-12 | 1996-11-14 | E.I. Du Pont De Nemours And Company | Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase |
US6361983B1 (en) | 1999-09-30 | 2002-03-26 | E. I. Du Pont De Nemours And Company | Process for the isolation of 1,3-propanediol from fermentation broth |
WO2001025178A1 (en) | 1999-10-05 | 2001-04-12 | E.I. Du Pont De Nemours And Company | Process to separate 1,3-propanediol or glycerol, or a mixture thereof from a biological mixture |
KR20020037064A (en) | 1999-10-05 | 2002-05-17 | 메리 이. 보울러 | Process to Separate 1,3-Propanediol or Glycerol, or a Mixture Thereof from a Biological Mixture |
US6603048B1 (en) | 1999-10-05 | 2003-08-05 | E. I. Du Pont De Nemours And Company | Process to separate 1,3-propanediol or glycerol, or a mixture thereof from a biological mixture |
US6428992B1 (en) | 1999-11-16 | 2002-08-06 | Roquette Freres | Process for the purification of 1,3-propanediol from a fermentation medium |
US20020133049A1 (en) | 2000-03-29 | 2002-09-19 | Archer-Daniels-Midland Company | Method of recovering 1,3-propanediol from fermentation broth |
JP2004229660A (en) | 2003-01-07 | 2004-08-19 | Osaka Industrial Promotion Organization | New protein and method for preparation of arabinobiose using the same |
Non-Patent Citations (1)
Title |
---|
Beibl et al, "Fermentation of glycerol to 1,3-propanediol: use of cosubstrates," 1995, vol. 44, pp. 15-19. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110060168A1 (en) * | 2008-03-02 | 2011-03-10 | Molzahn David C | Improved hydrogenation process |
US8324434B2 (en) | 2008-03-02 | 2012-12-04 | Dow Global Technologies, Llc | Hydrogenation process |
Also Published As
Publication number | Publication date |
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WO2006025697A1 (en) | 2006-03-09 |
US20080097130A1 (en) | 2008-04-24 |
KR20060020864A (en) | 2006-03-07 |
BRPI0514743B1 (en) | 2015-05-05 |
BRPI0514743A (en) | 2008-06-24 |
CN101010272A (en) | 2007-08-01 |
KR100629772B1 (en) | 2006-09-28 |
CN101010272B (en) | 2012-08-29 |
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